On the connection between structural distortion and magnetism in graphene with a single vacancy

• DFT was used to calculate the magnetic properties of a graphene sheet with a single vacancy.
• The link between structural distortion and magnetism in this system was investigated.
• The ground state of the system was found to be planar and magnetic.
• A systematic investigation of the effects of out-of-plane atomic shifts was performed.
• An out-of-plane distortion leads to nonmagnetic metastable solutions.

The correlation between structural distortion and emergence of magnetism in graphene containing a single vacancy was investigated using first-principles calculations based on density functional theory (DFT). Our results have shown that a local distortion is formed around the vacancy, with reconstruction of two atomic bonds and with a dangling bond remaining at the third atom adjacent to the vacancy. A systematic investigation of the possible out-of-plane displacement of this third atom was then carried out, in order to ascertain its effects on the magnetic features of the system. The ground state was definitely found to be magnetic and planar, with spin-resolved σσ and ππ bands contributing to the total magnetic moment. However, we have also found that metastable solutions can be achieved if an initial shift of the third atom above a minimum threshold from the graphene plane is provided, which leads to a nonplanar geometry and a nonmagnetic state.